Fluorotriazine-group-containing azo dyestuffs

ABSTRACT

Reactive dyestuffs of the formula ##STR1## wherein R, D, R 1 , R 2  and n have the meaning indicated in the description, 
     and their use for dyeing textile materials containing hydroxyl groups and textile materials containing nitrogen, in particular for textile materials made of natural and regenerated cellulose, in red shades.

The present invention relates to reactive dyestuffs of the formula##STR2## wherein

R is ##STR3##

D is the radical of a diazo component,

R₁ is H or alkyl,

R₂ is SO₃ H, SO₂ NHR₁, SO₂ NR₁ R₃, COOR₁, CONHR₁, CONR₁ R₃, CN, OH,halogen, alkyl, alkoxy, alkylcarbonylamino or ureido,

wherein

R₃ is alkyl, and

n=is 1, 2 or 3.

The alkyl and alkoxy radicals and the ureido radicals can be optionallysubstituted. Preferred alkyl and alkoxy radicals are those with 1-4 Catoms. Preferred radicals R₁ are hydrogen as well as CH₃ and C₂ H₅.Examples of the radicals R₂ are fluorine, chlorine and bromine, andfurthermore the groups: SO₃ H, SO₂ NH₂, SO₂ NHCH₃, SO₂ N(CH₃)₂, SO₂ NHC₂H₅, SO₂ NH--CH₂ --CH₂ OH, SO₂ N(CH₃)CH₂ --CH₂ OH, SO₂ --NH--CH₂ --CH₂--OSO₃ H, COOH, COOCH₃, COOC₂ H₅, CONH₂, CONHCH₃, CON(CH₃)₂, CONHC₂ H₅,CN, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, CH₂ --SO₃ H, CH₂ OH, CH₂ --COOH, OCH₃, OC₂H₅, O--C₂ H₄ --OH, O--CH₂ --CH₂ --OCH₃, O--CH₂ --CH₂ --OC₂ H₅,NH--COCH₃, NH--CO--CH₂ OH, NH--CO--CH₂ Cl, NH--CO--CH₂ --SO₃ H,NH--CO--NH₂, NH--CO--NH--CH₂ --CH₂ OH, NH--CO--NHCH₃ and NH--CON(CH₃)₂.

Preferred radicals R₃ are CH₃, C₂ H₅ and C₂ H₄ OH.

Preferred dyestuffs within the scope of the formula (I) are those of theformula ##STR4## as well as those of the formula ##STR5## andfurthermore those of the formula ##STR6## and those of the formula##STR7## and finally those of the formula ##STR8## wherein

X is 3-sulphophenyl, 4-methylphenyl or 3-hydroxyphenyl, and those of theformula ##STR9## wherein Y is 4-sulphophenyl, 4-acetylaminophenyl or3-hydroxyphenyl.

Dyestuffs of the formulae (II)-(V) with the substituent ##STR10## on thegroup ##STR11## are also preferred.

The dyestuffs of the formula (I) are obtained by a process in which1-amino-8-hydroxynaphthalene-disulphonic acids of the formula ##STR12##are first subjected to a condensation reaction with cyanuric fluoride togive compounds of the formula ##STR13## and these are then subjected toa condensation reaction with aromatic amines of the formula ##STR14##wherein R and R₁ have the meaning indicated above, to give compounds ofthe formula ##STR15## wherein R and R₁ have the meaning indicated, andthe reactive intermediate products of the formula (XI) are then coupledwith diazotised amines of the general formula

    D--NH.sub.2                                                (XII)

One variant of the preparation of compounds of the formula (XI) consistsin reacting cyanuric fluoride with the aromatic amines of the formula(X) to give reactive components of the formula ##STR16## and subjectingthese to a condensation reaction with theaminohydroxynaphthalenedisulphonic acids of the formula (VIII).

Further variants of the preparation of dyestuffs of the formula (I)consist in first coupling the intermediate products (IX) with diazoniumsalts to give difluorotriazinyl-azo dyestuffs of the formula ##STR17##and then subjecting these compounds (XIV) to a condensation reactionwith the amines (X), or subjecting azo dyestuffs of the formula##STR18## to a condensation reaction either with the reactive componentsof the formula (XIII), or stepwise with cyanuric fluoride to give thecompounds (XIV) and then subjecting these compounds to a condensationreaction with the aromatic amines (X) to give the dyestuffs (I).

Examples of compounds of the formula (VIII) are:1-amino-8-hydroxy-naphthalene-3,6-disulphonic acid,1-amino-8-hydroxy-naphthalene-4,6-disulphonic acid,1-amino-8-hydroxynaphthalene-3,5-disulphonic acid and1-amino-8-hydroxy-naphthalene-2,4-disulphonic acid.

Examples of aromatic amines of the formula (X) which are suitable forthe condensation reaction with the intermediate products (IX) or (XIV)are: 1-amino-3- or -4-methylbenzene, 1-amino-3,4- or-3,5-dimethylbenzene, 1-amino-3- or -4-ethylbenzene, 1-amino-3- or-4-methoxybenzene, 1-amino-4-ethoxybenzene, 1-amino-3- or-4-(2-hydroxyethoxy)-benzene, 1-amino-3- or-4-(2-methoxyethoxy)-benzene, 1-amino-3- or -4-chlorobenzene, 3- or4-amino-phenylmethanesulphonic acid, 3-aminobenzenesulphonic acid,4-aminobenzenesulphonic acid, 5-aminobenzene-1,3-disulphonic acid,4-aminobenzene-1,2-disulphonic acid,4-amino-5-methylbenzene-1,2-disulphonic acid, 3- or4-aminobenzenesulphonamide, 3- or 4-aminobenzenesulphonic acidmethylamide, 3- or 4-aminobenzenesulphonic acid dimethylamide, 3- or4-aminobenzenesulphonic acid (2-hydroxyethyl)amide,5-aminobenzene-1,3-dicarboxylic acid, 3- or 4-aminobenzoic acid, 3- or4-aminobenzamide, 3- or 4-aminobenzoic acid methyl ester or ethyl ester,3- or 4-aminobenzonitrile,3-amino-(N-phenylsulphonyl)-benzenesulphonamide, 3- or 4-aminophenol,5-amino-2-hydroxybenzenesulphonic acid,4-amino-2-hydroxybenzenesulphonic acid, 5-amino-2-ethoxybenzenesulphonicacid, 1-acetylamino-3- or -4-aminobenzene, 1-amino-3- or-4-(hydroxyacetyl)-aminobenzene, 1-amino-4-(sulphoacetyl)aminobenzene,3- or 4-aminophenylurea, N-(3-aminophenyl)-N'-(2-hydroxyethyl)-urea, 3-or 4-aminophenyloxamic acid, 1-methylamino-3- or -4-methylbenzene,1-ethylamino-4-chlorobenzene, 1-ethylamino-3- or -4-methylbenzene,-(2-hydroxyethyl)-amino-3-methylbenzene, 3- or 4-methylaminobenzoic acidand 4-methylaminobenzenesulphonic acid.

2-Aminonaphthalene-1-sulphonic acid, 4-aminonaphthalene-1-sulphonicacid, 5-aminonaphthalene-1-sulphonic acid,6-aminonaphthalene-1-sulphonic acid, 7-aminonaphthalene-1-sulphonicacid, 8-aminonaphthalene-1-sulphonic acid,1-aminonaphthalene-2-sulphonic acid, 4-aminonaphthalene-2-sulphonicacid, 5-aminonaphthalene-2-sulphonic acid,6-aminonaphthalene-2-sulphonic acid, 7-aminonaphthalene-2-sulphonicacid, 7-methylaminonaphthalene-2-sulphonic acid,7-ethylaminonaphthalene-2-sulphonic acid,7-butylaminonaphthalene-2-sulphonic acid,7-isobutylaminonaphthalene-2-sulphonic acid,8-aminonaphthalene-2-sulphonic acid, 4-aminonaphthalene-1,3-disulphonicacid, 5-aminonaphthalene-1,3-disulphonic acid,6-aminonaphthalene-1,3-disulphonic acid,7-aminonaphthalene-1,3-disulphonic acid,8-aminonaphthalene-1,3-disulphonic acid,2-aminonaphthalene-1,5-disulphonic acid,3-aminonaphthalene-1,5-disulphonic acid,4-aminonaphthalene-1,5-disulphonic acid,4-aminonaphthalene-1,6-disulphonic acid,8-aminonaphthalene-1,6-disulphonic acid,4-aminonaphthalene-1,7-disulphonic acid,3-aminonaphthalene-2,6-disulphonic acid,4-aminonaphthalene-2,6-disulphonic acid, 3-aminonaphthalene-2,7-disulphonic acid,4-aminonaphthalene-2,7-disulphonic acid,6-aminonaphthalene-1,3,5-trisulphonic acid,7-aminonaphthalene-1,3,5-trisulphonic acid,8-aminonaphthalene-1,3,5-trisulphonic acid,4-aminonaphthalene-1,3,6-trisulphonic acid,7-aminonaphthalene-1,3,6-trisulphonic acid,8-aminonaphthalene-1,3,6-trisulphonic acid and4-aminonaphthalene-1,3,7-trisulphonic acid.

Examples of diazotisable amines of the formula (XII) which may bementioned are: 2-aminobenzenesulphonic acid, 3-aminobenzenesulphonicacid, 4-aminobenzenesulphonic acid, 2-aminobenzene-1,4-disulphonic acid,4-aminobenzene-1,3-disulphonic acid,6-amino-5-methylbenzene-1,3-disulphonic acid,2-amino-5-methylbenzenesulphonic acid, 2-amino-5-methoxybenzenesulphonicacid, 2-amino-4-chlorobenzenesulphonic acid,2-amino-5-chlorobenzenesulphonic acid,2-amino-5-acetylaminobenzenesulphonic acid,2-amino-4-acetylaminobenzenesulphonic acid,3-amino-4-methoxybenzenesulphonic acid, 3-amino-4-methylbenzenesulphonicacid, 2-amino-3,5-dimethylbenzenesulphonic acid,4-amino-5-methylbenzene-1,2-disulphonic acid, 2-amino-4-sulphobenzoicacid, 2-amino-5-sulphobenzoic acid, 2-aminobenzoic acid, 4-aminobenzoicacid, 1-amino-2-, -3- or -4-methylbenzene, 1-aminobenzene, 1-amino-2-,-3- or -4-methoxybenzene, 1-amino-2-trifluoromethylbenzene,2-aminonaphthalene-1-sulphonic acid, 2-amino-naphthalene-1,5-disulphonicacid, 2-amino-naphthalene-1,7-disulphonic acid,3-amino-naphthalene-1,5-disulphonic acid,3-amino-naphthalene-2,6-disulphonic acid,2-amino-naphthalene-3,6-disulphonic acid, 7-amino-naphthalene-1,3-disulphonic acid, 6-amino-naphthalene-1,3-disulphonic acid,4-amino-naphthalene-1-sulphonic acid, 5-amino-naphthalene-1-sulphonicacid, 6-amino-naphthalene-1-sulphonic acid,1-amino-naphthalene-3,7-disulphonic acid,4-amino-naphthalene-1,3-disulphonic acid,6-amino-naphthalene-1,3,5-trisulphonic acid,7-amino-naphthalene-1,3,6-trisulphonic acid,4-amino-naphthalene-1,3,6-trisulphonic acid,4-aminophenyl-methanesulphonic acid, 1-amino-3- or-4-(sulphoacetyl)-aminobenzene and 1-amino-2-chlorobenzene.

The reaction of the compounds (VIII) or (XV) with cyanuric flouride iscarried out in an aqueous medium at temperatures from -10° to +10°,preferably 0° to +5°, in the presence of alkaline condensing agents,such as alkali metal hydroxide solutions, alkali metal carbonatesolutions, alkali metal bicarbonate solutions, alkali metal phosphatesolutions or alkali metal hydrogen phosphate solutions, at pH values of2-7, but preferably 3-5.

The further condensation of the compounds (IX) or (XIV) with the aminesof the formula (X) is carried out in an aqueous medium at temperaturesfrom -10° to +40°, preferably in the range from 0° to +20°, and at pHvalues of 4-8. The condensation of the compounds (VIII) or (XV) with thereactants (XIII) can also be carried out under these conditions in anaqueous or aqueous-organic medium.

A particularly advantageous and economical process variant consists incarrying out all the process steps successively, without isolating theintermediate stages.

The new dyestuffs are extremely valuable products which are suitable forthe most diverse application purposes. They are of preferred interestfor dyeing textile materials containing hydroxyl groups and textilematerials containing nitrogen, in particular for textile materials madeof natural and regenerated cellulose, in red shades. Because of thereactive fluorine substituent in the triazine ring, the products areexceptionally suitable for use as reactive dyestuffs for dyeingcellulose materials in accordance with the dyeing techniques which havebeen disclosed for these materials, and especially for dyeing thesematerials from a long liquor by the exhaustion process.

The formulae given are those of the free acids. In general, their saltsare employed for dyeing, in particular the alkali metal salts (forexample Na salts, K salts and Li salts) or also the ammonium salts. Thedyestuffs are also generally isolated in the form of the salts.

The temperature data are in °C.

EXAMPLE 1

127.6 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 1,600 ml of water at pH 5.5. After cooling the solution to0°-5°, 34.2 ml of cyanuric fluoride are added dropwise in the course of30 minutes and the pH value of the solution is kept at 4.0-4.5 by meansof 20% strength sodium carbonate solution. When the reaction has ended,a neutralised solution of 69.5 g of 4-aminobenzenesulphonic acid in 300ml of water is added dropwise and the pH value is kept at 4.8-5.0,whilst keeping the mixture at 0°-5°. The mixture is further stirredunder these conditions for about 1 hour, until the condensation reactionhas ended and no more sodium carbonate solution is consumed.

89.2 g of 2-aminonaphthalene-1-sulphonic acid are dissolved in 1,000 mlof water at pH 7. The solution is cooled to 0°-5°, 80 ml of concentratedhydrochloric acid are added and 100 ml of 4N sodium nitrite solution areadded dropwise. The mixture is subsequently stirred at 0°-5° for halfand hour and any excess of nitrite still present is destroyed withamidosulphonic acid solution.

The diazonium salt solution is slowly added to the solution of thereactive component prepared above and coupling is carried out at pH7.5-8.0 and at 0°-10°. The temperature is allowed to rise to 20°, the pHvalue is adjusted to 5.0 with 10% strength hydrochloric acid and thedyestuff is salted out with 400 g of sodium chloride. It is filteredoff, washed with 20% strength sodium chloride solution and dried at 40°in vacuo.

In the form of the free acid, the dyestuff corresponds to the formula##STR19##

50 g of cotton hanks are dyed in 1 liter of a dye liquor, which contains1.5 g of the above dyestuff, by heating the liquor to 40° in the courseof 30 minutes, adding 50 g of sodium sulphate in several portions, thenadding 20 g of sodium carbonate and treating the material at thistemperature for 60 minutes.

After rinsing, soaping at the boil and drying, a bluish-tinged reddyeing which has good fastness to light and is very fast to wetprocessing is obtained.

EXAMPLE 2

63.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 800 ml of water at pH 5.5 and the solution is cooled to0°-5°. 18.2 ml of cyanuric fluoride are added dropwise in the course of15 minutes, and during this the pH value in the solution is kept at4.0-4.5 with sodium carbonate solution. The mixture is subsequentlystirred under the same conditions for 1/2 hour and a solution which hasbeen prepared by dissolving 34.6 g of 3-aminobenzenesulphonic acid in150 ml of water at pH 6.0 is then added dropwise. The pH value isadjusted to 5.5 and the temperature is further kept at 0°-5°. Thecondensation reaction has ended after about 1 hour.

38.1 g of 2-aminobenzenesulphonic acid are dissolved in 400 ml of waterat pH 6.5. After adding 40 ml of concentrated hydrochloric acid andcooling the mixture to 0°-5°, the amine is diazotised by adding 55 ml of4N sodium nitrite solution dropwise. When the diazotisation has ended,after 178 -1 hour, excess nitrite is removed with amidosulphonic acidsolution.

The diazo compound thus obtained is now added dropwise, at 0°-10°, tothe coupling component obtained above and the pH value is kept at7.0-7.5 with sodium carbonate solution. When the coupling has ended, thetemperature is allowed to rise to 20°, the pH value is adjusted to 6.0with 10% strength hydrochloric acid and the dyestuff, which precipitatesin the form of small needles, is salted out with 200 g of sodiumchloride. The precipitate is subsequently stirred for 1 hour andfiltered off and the dyestuff cake is washed with 700 ml of 15% strengthsodium chloride solution.

After drying the cake at 40° in vacuo, the dyestuff of the formula##STR20## which dyes cotton, by the dyeing process described in Example1, in somewhat bluish-tinged red shades which are fast to wetprocessing, is obtained.

EXAMPLE 3

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 200 ml of water at pH 5.8. After cooling the solution to0°-5°, 3.8 g of cyanuric fluoride are added dropwise in the course of 10minutes, and during this the pH value of the solution is kept at 4.0-4.5by adding 20% strength sodium carbonate solution dropwise. The mixtureis subsequently stirred for about 15 minutes and 4.3 g of m-toluidineare then added. The pH value is now kept at 5.5-6.0. After thecondensation of the difluorotriazinyl component with the m-toluidine hasended, a diazonium salt suspension which has been obtained from 7.0 g of2-aminobenzenesulphonic acid in 100 ml and 20 ml of concentratedhydrochloric acid with 20 ml of 2N sodium nitrite solution analogouslyto Example 2, is allowed to run in at 0°-5°.

The coupling is carried out at pH 7.0-7.5 and at 0°-10°. Finally, thetemperature is allowed to rise to 20° C., the pH value is adjusted to6.0, the dyestuff which has precipitated is further salted out with 100g of sodium chloride and the suspension is subsequently stirred for 2hours. After filtering off the dyestuff and washing the filter cake with400 ml of 15% strength sodium chloride solution and finally with 200 mlof 10% strength sodium chloride solution, a dyestuff of the formula##STR21## is obtained and is dried at 40° in vacuo.

The dyestuff dyes cellulose materials, by the dyeing process indicatedin Example 1, in somewhat bluish-tinged red shades which are fast tolight and very fast to wet processing.

EXAMPLE 4

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 200 ml of water at pH 5.8 and, after cooling the solutionto 0°-5°, are subjected to a condensation reaction with 3.8 ml ofcyanuric fluoride, which is added dropwise, at pH 4.0-4.5. Aftersubsequently stirring the mixture for 1/4 of an hour, 4.4 g of3-aminophenol are added and the pH value is then kept at 5.5-6.0. Thetemperature is allowed to rise to 20° in the course of 1 hour and thereaction is brought to completion.

8.9 g of 2-aminonaphthalene-1-sulphonic acid are dissolved in 150 ml ofwater at pH 7, 20 ml of concentrated hydrochloric acid are added and themixture is cooled to 0°-5°. 20 ml of 2N sodium nitrite solution are thenadded dropwise. After subsequently stirring the mixture for one hour,excess nitrite is destroyed with amindosulphonic acid solution.

After renewed cooling of the solution, prepared above, of the couplingcomponent, the diazonium compound is allowed to run in at 0°-10° and thepH value is kept at 7.5-8.0 for the coupling. The mixture is then warmedto 20° and adjusted to pH 5.0 with hydrochloric acid and the dyestuff isfiltered off. The filter cake is washed with 10% strength sodiumchloride solution until the runnings are almost colourless. Thedyestuff, which corresponds to the formula ##STR22## is dried at 40° invacuo.

It dyes cotton, from a long liquor, in bluish-tinged red shades whichhave excellent fastness to wet processing.

EXAMPLE 5

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved at pH 5.8 and are reacted with 3.8 ml of cyanuric fluoride asdescribed in Example 3. 6.0 g of 4-aminoacetanilide are added to theresulting solution, the pH value is adjusted to 5.5-6.0 and thetemperature is allowed to rise gradually from 0°-5° to 20°.

After the condensation has ended, the mixture is cooled again to 0°-5°and a suspension of the diazonium compound which has been obtained bydiazotising 8.9 g of 2-aminonaphthalene-1-sulphonic acid as in Example 4is allowed to run in. The coupling is carried out at pH 7.5-8.0 and at0°-10°, the pH value in the suspension of crystals is then adjusted to5.0 and the dyestuff is salted out still further with 50 g of sodiumchloride, filtered off, washed with 15% strength sodium chloride untilthe runnings are almost colourless and dried at 40° in vacuo.

The resulting dyestuff corresponds to the formula ##STR23##

It dyes cotton, for example by the exhaustion process as is described inExample 1, in bluish-tinged red shades which have very good fastness towet processing.

EXAMPLE 6

63.8 g of 1-amino-8-hydroxy-3,6-disulphonic acid are dissolved in 800 mlof water at pH 5.5 with sodium hydroxide solution, and the solution iscooled to 0°-5°. 18.2 ml of cyanuric fluoride are uniformly addeddropwise to this solution in the course of about 15 minutes and the pHvalue is kept at 4.0-4.5 by adding 20% strength sodium carbonatesolution dropwise. At the same time, intensive cooling ensures that thetemperature does not rise above +5°. After the addition has ended, themixture is subsequently stirred for about 15 minutes and a solution of21.4 g of p-toluidine in 50 ml of acetone is then added dropwise in thecourse of a further 15 minutes. The pH value is kept at 5.5-6.0, thetemperature is allowed to rise to 20° in the course of about 2 hours andthe condensation reaction is brought to completion.

38.1 g of 2-aminobenzenesulphonic acid are diazotised in 400 ml of waterand 40 ml of concentrated hydrochloric acid with 55 ml of 4N sodiumnitrite solution as in Example 2.

The resulting diazonium salt suspension is uniformly added to thecoupling component, prepared above, at 0°-10° in the course of about 15minutes and the pH value is kept at 7.0-7.5 with 20% strength sodiumcarbonate solution for the purpose of coupling. After the coupling hasended, the temperature is allowed to rise to 20°, the pH value isadjusted to 5.0 with hydrochloric acid and the dyestuff is furthersalted out with 50 g of sodium chloride. The dyestuff is filtered off,washed with 10% strength sodium chloride solution until the runnings areslightly coloured, and dried at 50° in vacuo. It corresponds to theformula ##STR24## and dyes cotton, by the dyeing process of Example 1,in somewhat bluish-tinged red shades which have good fastness to lightand wet processing.

EXAMPLE 7

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid in 200 ml ofwater are subjected to a condensation reaction with 3.8 ml of cyanuricfluoride at pH 4.0-4.5 and at 0°-5° as described in Example 3. 7.0 g of4-aminobenzenesulphonic acid are added to the resulting solution and thepH value in the reaction mixture is kept at 5.5-6.0. The mixture issubsequently stirred at 0°-5° for one hour. A diazonium salt suspensionwhich has been obtained from 7.0 g of 2-aminobenzenesulphonic acid in100 ml of water and 20 ml of concentrated hydrochloric acid with 20 mlof 2N sodium nitrite solution at 0°-5° is then allowed to run in and thepH value is kept at 7.0-7.5 and the temperature at 0°-10° for thecoupling. Finally, the temperature is increased to 20° in the course of1 hour. After the coupling has ended, the dyestuff is salted out byadding 100 g of sodium chloride, filtered off and washed with 20%strength sodium chloride solution until the runnings are almostcolourless. The dyestuff, which, in the form of the free acid,corresponds to the formula ##STR25## is dried at 40° in vacuo.

It dyes cotton, by the dyeing process of Example 1, in somewhatbluish-tinged red shades which have excellent fastness to wet processingand good fastness to light.

EXAMPLE 8

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 200 ml of water and subjected to a condensation reactionwith 3.8 ml of cyanuric fluoride at pH 4.0-4.5 and at 0°-5° as inExample 3. 6.0 g of 4-aminoacetanilide are then added and the pH valueof the reaction mixture is kept at 5.5-6.0 with 20% strength sodiumcarbonate solution. The temperature is allowed to rise to 20° in thecourse of 2 hours and the mixture is then cooled again to below +10°.

7.0 g of 2-aminobenzenesulphonic acid are dissolved in 100 ml of waterat 0°-5°, with neutralisation, and, after adding 20 ml of concentratedhydrochloric acid, are diazotised with 20 ml of 2N sodium nitritesolution. After destroying any excess of nitrite, the diazonium saltsuspension is slowly added to the solution, obtained above, of thecoupling component and the pH value is kept at 7.0-7.5. The temperatureis allowed to rise to 20° in the course of a few hours and, after thecoupling has ended, the dyestuff is salted out with 100 g of sodiumchloride. The needles of the dyestuff which have precipitated arefiltered off and washed with 10% strength sodium chloride solution. Thedyestuff is dried at 50° in vacuo. It corresponds to the formula##STR26## and dyes cotton, by the dyeing process of Example 1, insomewhat bluish-tinged red shades which have excellent fastness to lightand wet processing.

EXAMPLE 9

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 200 ml of water at pH 5.8 and are reacted with 3.8 ml ofcyanuric fluoride at 0°-5° and pH 4.0-4.5 as described in Example 3.After the reaction has ended, a solution of 4.9 g of p-anisidine in 15ml of acetone is added dropwise and the pH value in the reaction mixtureis kept at 5.5-6.0.

7.0 g of 2-aminobenzenesulphonic acid are dissolved in 100 ml of waterat pH 6. 20 ml of concentrated hydrochloric acid are added to thesolution, the mixture is cooled to 0°-5° and the amine is diazobised byadding 20 ml of 2N sodium nitrite solution dropwise. The mixture issubsequently stirred until the diazotisation has ended, and any excessof nitrite is destroyed with amidosulphonic acid.

The suspension of the diazonium salt is now slowly added to the couplingcomponent prepared above and the coupling is carried out at 0°-10° andpH 7.0-7.5. Finally, the temperature is allowed to rise to 20°, the pHvalue is adjusted to 6.0 with 10% strength hydrochloric acid and thedyestuff which has precipitated during the coupling is further saltedout with 200 g of sodium chloride. After subsequently stirring themixture for one hour, the small needles of the dyestuff, whichcorresponds to the formula ##STR27## are filtered off, washed with 700ml of 15% strength sodium chloride solution and 200 ml of 10% strengthsodium chloride solution and dried at 40° in vacuo.

On cotton, by the process of Example 1, the dyestuff gives somewhatbluish-tinged red dyeings which have excellent fastness to wetprocessing and good fastness to light.

EXAMPLE 10

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 200 ml of water at pH 5.5 and are subjected to acondensation reaction with 3.8 ml of cyanuric fluoride at 0°-5° and pH4.0-4.5 according to Example 3. 4.4 g of 3-aminophenol are added to thesolution of the condensation product and the pH value is adjusted to5.5-6.0. The temperature is allowed to rise to 20° in the course of afew hours, whilst maintaining this pH value with the aid of 20% strengthsodium carbonate solution, and after the reaction has ended the mixtureis cooled again to below +10°.

7.0 g of 2-aminobenzenesulphonic acid are dissolved in 150 ml of waterat 0°-5° and pH 7 and, after adding 20 ml of concentrated hydrochloricacid, are diazotised with 20 ml of 2N sodium nitrite solution. After thediazotisation has ended and excess nitrite has been destroyed withamidosulphonic acid, the suspension of the diazonium salt is allowed torun uniformly into the reactive coupling component prepared above andthe pH value is kept at 7.0-7.5 for the purpose of coupling. After thecoupling has ended, the mixture is warmed to 20° and adjusted to pH 5.0with hydrochloric acid and the dyestuff which has partially precipitatedis further salted out with 50 g of sodium chloride. It is filtered off,washed with 10% strength sodium chloride solution and dried at 50° invacuo.

In the form of the free acid, it corresponds to the formula ##STR28##

It dyes cotton, from a long liquor, in somewhat bluish-tinged red shadeswhich have very good fastness to light and wet processing.

EXAMPLE 11

16.0 g of 1-amino-8-hydroxynaphthalene-4,6-disulphonic acid aredissolved in 200 ml of water at pH 6.0. The solution is cooled to 0°-5°and the pH value is adjusted to 3.5 with concentrated hydrochloric acid.4.7 ml of cyanuric fluoride are added dropwise in the course of 10minutes and the pH value is kept at 3.5-4.0 with 20% strength sodiumcarbonate solution. The mixture is subsequently stirred at 0°-5° and pH4.0 for 15 minutes and 8.7 g of 3-aminobenzenesulphonic acid are thenadded. The condensation reaction between the difluorotriazinyl compoundand the 3-aminobenzenesulphonic acid is brought to completion byadjusting the pH value to 5.5-6.0.

11.2 g of 2-aminonaphthalene-1-sulphonic acid are dissolved in 170 ml ofwater at pH 7. After cooling the solution to 0°-5° and adding 20 ml ofconcentrated hydrochloric acid, 25 ml of 2N sodium nitrite solution areadded dropwise, the mixture is subsequently stirred for a further 1 hourat 0°-5° and excess nitrite is destroyed with amidosulphonic acid.

The diazonium salt suspension is slowly added, at 0°-10°, to thecoupling component prepared above. The pH value is kept at 7.5-8.0 with20% strength sodium carbonate solution and the temperature is allowed torise to 20° in the course of 1 hour. The mixture is adjusted to pH 6.0with hydrochloric acid and the dyestuff is salted out with 150 g ofsodium chloride, filtered off, washed with 15% strength sodium chloridesolution and dried at 50° in vacuo. It corresponds to the formula##STR29## and dyes cotton, by the dyeing process of Example 1, inbluish-tinged red shades which have good fastness to light and very goodfastness to wet processing.

EXAMPLE 12

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 200 ml of water at pH 5.5 and are subjected to acondensation reaction with 3.8 ml of cyanuric fluoride, which has beenadded dropwise, at 0°-5°, the pH value in the reaction mixture beingkept at 4.0-4.5 with 20% strength sodium carbonate solution during thecondensation. After the reaction has ended, a solution of 4.7 g ofp-toluidine in 10 ml of acetone is added dropwise, the pH value is nowkept at 5.5-6.0 and the temperature is allowed to rise gradually to 20°in the course of 2 hours, after which the condensation reaction betweenthe difluorotriazinyl compound and the p-toluidine has ended. Themixture is again cooled to 0°-10°.

12.1 g of 2-aminonaphthalene-1,5-disulphonic acid are dissolved in 150ml of water at pH 6.0. The solution is cooled to 0°-5°, 20 ml ofconcentrated hydrochloric acid are added and the amine is diazotised byadding 20 ml of 2N sodium nitrite solution dropwise. After subsequentlystirring the mixture at 0°-5° for one hour, excess nitrite is destroyedwith amidosulphonic acid.

The diazonium compound is now slowly added to the suspension of thecoupling component prepared above and the pH value in the couplingsolution is kept at 7.0-7.5 with 20% strength sodium carbonate solution.After the coupling has ended, the temperature is allowed to rise to 20°,the pH value is adjusted to 5.0 with hydrochloric acid and the dyestuffis slowly salted out with 100 g of sodium chloride. The dyestuff isfiltered off, washed with 15% strength sodium chloride solution anddried at 50° in vacuo. It corresponds to the formula ##STR30## and dyescotton, from a long liquor, in bluish-tinged red shades which have goodfastness to light and very good fastness to wet processing.

EXAMPLE 13

If the 3-aminobenzenesulphonic acid in Example 11 is replaced by 8.7 gof 4-aminobenzenesulphonic acid and the procedure in all the reactionsteps is as described in that Example, a dyestuff of the formula##STR31## which has very similar coloristic properties to the dyestuffof Example 11 is obtained.

EXAMPLE 14

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid are firstreacted, under the conditions given in Example 12, with 3.8 ml ofcyanuric fluoride and the intermediate product formed is then subjectedto a condensation reaction with 4.7 g of p-toluidine.

10.1 g of 2-aminobenzene-1,4-disulphonic acid are dissolved in 130 ml ofwater at pH 6. 15 ml of concentrated hydrochloric acid are added and 20ml of 2N sodium nitrite solution are added dropwise at 0°-5°. Themixture is subsequently stirred for a further 1 hour and any excess ofnitrite is destroyed with amidosulphonic acid.

The diazonium compound thus prepared is allowed to run into the abovereactive coupling component at 0°-10° and the pH value is kept at7.0-7.5 for the purpose of coupling. After the diazo component has beenadded, the mixture is subsequently stirred for about a further 1 hour,the temperature is then allowed to rise to 20° and the pH value isadjusted to 5.0. The dyestuff is salted out with 150 g of sodiumchloride, filtered off, washed with 15% strength sodium chloridesolution and dried at 50° in vacuo. It corresponds to the formula##STR32## and dyes cotton in somewhat bluish-tinged red shades whichhave very good fastness to light and wet processing.

Further dyestuffs of the general formula ##STR33## are built upaccording to the methods described in the preceding Examples by acondensation reaction between the1-amino-8-hydroxynaphthalenedisulphonic acids listed in Table I,cyanuric fluoride and the aromatic amines ##STR34## and subsequentcoupling of the resulting reactive coupling components with thediazotised amines D-NH₂.

                                      TABLE 1                                     __________________________________________________________________________                                   Aromatic amine                                  No.                                                                              Diazo component  D-NH.sub.2                                                               1-Amino-8-hydroxynaphthalene- disulphonic                                                     ##STR35##                                     __________________________________________________________________________    15 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 3-Aminoacetanilide                                sulphonic acid                                                                            3,6-disulphonic acid                                           16 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-benzenesulphonamide                       sulphonic acid                                                                            3,6-disulphonic acid                                           17 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-methylbenzene                           sulphonic acid                                                                            3,6-disulphonic acid                                           18 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 5-Amino-2-ethoxybenzene-                          sulphonic acid                                                                            3,6-disulphonic acid                                                                          sulphonic acid                                 19 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-methoxybenzene                          sulphonic acid                                                                            3,6-disulphonic acid                                           20 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Aminophenylmethanesulphonic                     sulphonic acid                                                                            3,6-disulphonic acid                                                                          acid                                           21 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 5-Amino-2-hydroxybenzene-                         sulphonic acid                                                                            3,6-disulphonic acid                                                                          sulphonic acid                                 22 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Amino-2-hydroxybenzene-                         sulphonic acid                                                                            3,6-disulphonic acid                                                                          sulphonic acid                                 23 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzoic acid                               sulphonic acid                                                                            3,6-disulphonic acid                                           24 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           1-sulphonic acid                                                                          3,6-disulphonic acid                                           25 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminoacetanilide                                1-sulphonic acid                                                                          3,6-disulphonic acid                                           26 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene                                                                  5-Amino-2-ethoxybenzene-                          1-sulphonic acid                                                                          3,6-disulphonic acid                                                                          sulphonic acid                                 27 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-hydroxyacetylamino-                     1-sulphonic acid                                                                          3,6-disulphonic acid                                                                          benzene                                        28 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 2-Amino-4-sulphobenzoic acid                      1-sulphonic acid                                                                          3,6-disulphonic acid                                           29 2-Aminobenzene-1,4-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 4-Amino-benzoic acid ethyl                        disulphonic acid                                                                          3,6-disulphonic acid                                                                          ester                                          30 2-Aminobenzene-1,4-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminophenol                                     disulphonic acid                                                                          3,6-disulphonic acid                                           31 2-Aminobenzene-1,4-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methoxybenzene                          disulphonic acid                                                                          3,6-disulphonic acid                                           32 4-Aminobenzene-1,3-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminophenylurea                                 disulphonic acid                                                                          3,6-disulphonic acid                                           33 4-Aminobenzene-1,3-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           disulphonic acid                                                                          3,6-disulphonic acid                                           34 4-Aminobenzene-1,3-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphamide                          disulphonic acid                                                                          3,6-disulphonic acid                                           35 2-Amino-4-acetyl-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzoic acid                               aminobenzene-                                                                             3,6-disulphonic acid                                              sulphonic acid                                                             36 2-Amino-4-acetyl-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      aminobenzene-                                                                             3,6-disulphonic acid                                              sulphonic acid                                                             37 2-Amino-4-acetyl-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           aminobenzene-                                                                             3,6-disulphonic acid                                              sulphonic acid                                                             38 2-Amino-5-chloro-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonic acid                      benzenesulphonic                                                                          3,6-disulphonic acid                                              acid                                                                       39 2-Amino-5-sulpho-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      benzoic acid                                                                              3,6-disulphonic acid                                           40 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 3-Methylaminobenzenesulphonic                     sulphonic acid                                                                            3,6-disulphonic acid                                                                          acid                                           41 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 3-Aminophenyloxamic acid                          sulphonic acid                                                                            3,6-disulphonic acid                                           42 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-(2-hydroxyethoxy)-                      sulphonic acid                                                                            3,6-disulphonic acid                                                                          benzene                                        43 2-Amino-5-methoxy-                                                                        1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      benzenesulphonic                                                                          3,6-disulphonic acid                                              acid                                                                       44 2-Amino-5-methoxy-                                                                        1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3,4-dimethylbenzene                       benzenesulphonic                                                                          4,6-disulphonic acid                                              acid                                                                       45 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           sulphonic acid                                                                            4,6-disulphonic acid                                           46 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-methylbenzene                           sulphonic acid                                                                            4,6-disulphonic acid                                           47 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      sulphonic acid                                                                            4,6-disulphonic acid                                           48 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzene acid methyl                        sulphonic acid                                                                            4,6-disulphonic acid                                                                          ester                                          49 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonic acid                      sulphonic acid                                                                            4,6-disulphonic acid                                           50 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Aminophenylurea                                 sulphonic acid                                                                            4,6-disulphonic acid                                           51 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Aminoacetanilide                                sulphonic acid                                                                            4,6-disulphonic acid                                           52 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methoxybenzene                          sulphonic acid                                                                            4,6-disulphonic acid                                           53 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-chlorobenzene                           sulphonic acid                                                                            4,6-disulphonic acid                                           54 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzonitrile                               sulphonic acid                                                                            4,6-disulphonic acid                                           55 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzamide                                  sulphonic acid                                                                            4,6-disulphonic acid                                           56 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonamide                        1-sulphonic acid                                                                          4,6-disulphonic acid                                           57 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      1-sulphonic acid                                                                          4,6-disulphonic acid                                                                          (2-hydroxyethyl)-amide                         58 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methoxyethoxybenzene                    1-sulphonic acid                                                                          4,6-disulphonic acid                                           59 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonamide                        1-sulphonic acid                                                                          4,6-disulphonic acid                                           60 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Amino-N(phenylsulphonyl)-                       1-sulphonic acid                                                                          4,6-disulphonic acid                                                                          benzenesulphonamide                            61 2-Aminonaphthalene                                                                        1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-methoxybenzene                          1-sulphonic acid                                                                          4,6-disulphonic acid                                           62 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-(2-hydroxyethoxy)-                      1-sulphonic acid                                                                          4,6-disulphonic acid                                                                          benzene                                        63 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-methylbenzene                           1-sulphonic acid                                                                          4,6-disulphonic acid                                           64 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Aminobenzenesulphonic acid                      1-sulphonic acid                                                                          4,6-disulphonic acid                                                                          dimethylamide                                  65 2-Aminobenzene-1,4-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-methylbenzene                           disulphonic acid                                                                          4,6-disulphonic acid                                           66 4-Aminobenzene-1,3-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           disulphonic 4,6-disulphonic acid                                           67 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methoxybenzene                          1,5-disulphonic acid                                                                      4,6-disulphonic acid                                           68 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           1,5-disulphonic acid                                                                      4,6-disulphonic acid -69                                                                      2-Aminonaphthalene- 1-Amino-8-hydroxynaphth                                   alene- 1-Amino-3-methylbenzene                    1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           70 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3,4-dimethylbenzene                       1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           71 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           72 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-ethoxybenzene                           1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           73 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonic acid                      1,5-disulphonic acid                                                                      3,6-disulphonic acid                                                                          methylamide                                    74 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Methylamino-3-methylbenzene                     1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           75 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 4-Methylaminobenzoic acid                         1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           76 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminoacetanilide                                1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           77 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methoxybenzene                          1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           78 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 5-Amino-2-ethoxybenzenesulphonic                  1,5-disulphonic acid                                                                      3,6-disulphonic acid                                                                          acid                                           79 2-Amino-5-chloro-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 5-Amino-2-methylbenzenesulphonic                  benzenesulphonic                                                                          3,6-disulphonic acid                                                                          acid                                              acid                                                                       80 2-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 3-Methylamino-4-methylbenzene-                    sulphonic acid                                                                            3,6-disulphonic acid                                                                          sulphonic acid                                 81 5-Acetylamino-2-                                                                          1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      aminobenzene-                                                                             3,6-disulphonic acid                                              sulphonic acid                                                             82 4-Acetylamino-2-                                                                          1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      aminobenzene-                                                                             4,6-disulphonic acid                                              sulphonic acid                                                             83 2-Aminobenzene-1,4-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           disulphonic acid                                                                          4,6-disulphonic acid                                           84 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthlene-                                                                  1-Amino-3,4-dimethylbenzene                       sulphonic acid                                                                            4,6-disulphonic acid                                           85 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthlene-                                                                  1-Amino-3-chlorobenzene                           sulphonic acid                                                                            4,6-disulphonic acid                                           86 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 3-Aminophenylmethanesulphonic                     sulphonic acid                                                                            4,6-disulphonic acid                                                                          acid                                           87 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 3-Amino-5,6-dimethylbenzene-                      sulphonic acid                                                                            4,6-disulphonic acid                                                                          sulphonic acid                                 88 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 5-Amino-2-methylbenzene-                          sulphonic acid                                                                            3,6-disulphonic acid                                                                          sulphonic                                      89 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 3-Aminophenol                                     sulphonic acid                                                                            3,5-disulphonic acid                                           90 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      sulphonic acid                                                                            3,5-disulphonic acid                                           91 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           sulphonic acid                                                                            3,5-disulphonic acid                                           92 2-Aminobenzene-1-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 4-Aminoacetanilide                                sulphonic acid                                                                            3,5-disulphonic acid                                           93 2-Aminobenzene-1,4-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-methylbenzene                           disulphonic acid                                                                          3,5-disulphonic acid                                           94 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonic acid                      1-sulphonic acid                                                                          3,5-disulphonic acid                                           95 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           1,5-disulphonic acid                                                                      3,5-disulphonic acid                                           96 2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methoxybenzene                          1,5-disulphonic acid                                                                      3,5-disulphonic acid                                           97 4-Aminobenzene-1,3-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           disulphonic acid                                                                          3,5-disulphonic acid                                           98 4-Aminobenzene-1,3-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-3-hydroxyacetylamino-                     disulphonic acid                                                                          3,5-disulphonic acid                                                                          benzene                                        99 2-Amino-4-acetyl-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonic acid                      aminobenzenesulphonic                                                                     3,5-disulphonic acid                                              acid                                                                       100                                                                              2-Amino-4-acetyl-                                                                         1-Amino-8-hydroxynaphthalene-                                                                    "                                              aminobenzenesulphonic                                                                     3,6-disulphonic acid                                              acid                                                                       101                                                                              3-aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           102                                                                              3-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           1,5-disulphonic acid                                                                      3,6-disulphonic acid                                           103                                                                              4-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonic acid                      sulphonic acid                                                                            3,6-disulphonic acid                                           104                                                                              3-Aminobenzene-                                                                           1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      sulphonic acid                                                                            3,6-disulphonic acid                                           105                                                                              4-Aminobenzene-                                                                           1-Amino-8-hydroxynapthalene-                                                                     "                                              sulphonic acid                                                                            3,6-disulphonic acid                                           106                                                                              6-Amino-5-methyl-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           benzene-1,3-                                                                              3,6-disulphonic acid                                              disulphonic acid                                                           107                                                                              2-Amino-5-methyl-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      benzenesulphonic                                                                          3,6-disulphonic acid                                              acid                                                                       108                                                                              2-Amino-4-chloro-                                                                         1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonic acid                      benzenesulphonic                                                                          3,6-disulphonic acid                                              acid                                                                       109                                                                              2-Amino-3,5-di-                                                                           1-Amino-8-hydroxynaphthalene-                                                                    "                                              methylbenzene-                                                                            3,6-disulphonic acid                                              sulphonic acid                                                             110                                                                              2-Aminobenzoic                                                                            1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      acid        3,6-disulphonic acid                                           111                                                                              2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           1,7-disulphonic acid                                                                      3,6-disulphonic acid                                           112                                                                              2-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      3,6-disulphonic acid                                                                      3,6-disulphonic acid                                           113                                                                              4-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 4-Aminobenzenesulphonic acid                      1-sulphonic acid                                                                          3,6-disulphonic acid                                           114                                                                              4-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methoxybenzene                          1,3-disulphonic acid                                                                      3,6-disulphonic acid                                           115                                                                              7-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 1-Amino-4-methylbenzene                           1,3,6-trisulphonic                                                                        3,6-disulphonic acid                                              acid                                                                       116                                                                              Aniline     1-Amino-8-hydroxynaphthalene-                                                                 5-Aminobenzene-1,3-disulphonic                                3,6-disulphonic acid                                                                          acid                                           117                                                                              1-Amino-4-(sulpho-                                                                        1-Amino-8-hydroxynaphthalene-                                                                 3-Aminobenzenesulphonic acid                      acetyl)-aminobenzene                                                                      3,6-disulphonic acid                                           118                                                                              3-Aminonaphthalene-                                                                       1-Amino-8-hydroxynaphthalene-                                                                 3-Aminophenol                                     2,6-disulphonic                                                                           4,6-disulphonic acid                                              acid                                                                       119                                                                              2-Aminobenzene-                                                                           1-Amino-8-hydroxy-2,4-                                                                        3-Aminobenzenesulphonic acid                      sulphonic acid                                                                            disulphonic acid                                               120                                                                              2-Aminobenzene-                                                                           1-Amino-8-hydroxy-2,4-                                                                        1-Amino-4-methylbenzene                           sulphonic acid                                                                            disulphonic acid                                               121                                                                              2-Aminonaphthalene-                                                                       1-Amino-8-hydroxy-2,4-                                                                        4-Aminobenzenesulphonic acid                      1-sulphonic acid                                                                          disulphonic acid                                               __________________________________________________________________________

EXAMPLE 122

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 200 ml of water at pH 5.8 and the solution is cooled to0°-5°. 3.8 ml of cyanuric fluoride are uniformly added dropwise in thecourse of 10 minutes and the pH value in the solution is kept at 4.0-4.5with 20% strength sodium carbonate solution. After the condensationreaction has ended, 7.0 g of 3-aminobenzenesulphonic acid are added tothe mixture and the pH value is now kept at 5.5-6.0. 8.9 g of2-aminonaphthalene-1-sulphonic acid are dissolved in 150 ml of water ofpH 7, the solution is cooled to 0°-5° and 20 ml of concentrationhydrochloric acid are added. The diazotisation is now carried out byadding 20 ml of 2N sodium nitrite solution drowise. The diazonium saltsuspension formed is subsequently stirred at 0°-5° for a further 1 hourand any nitrite still present is destroyed with amidosulphonic acid.

The suspension, thus obtained, of the diazonium salt is allowed to runslowly into the solution, prepared above, of the coupling component at0°-10°, and during this the pH value in the coupling solution is kept at7.5-8.0. The temperature is then allowed to rise to 20° in the course ofabout 2 hours, the mixture is adjusted to pH 6.5 with hydrochloric acidand the dyestuff which has precipitated is filtered off and washed with5% strength sodium chloride solution.

The dyestuff, which corresponds to the formula ##STR36## is dried at 50°in vacuo. It dyes cotton, from a long liquor, in bluish-tinged redshades which have good fastness to light and very good fastness to wetprocessing.

EXAMPLE 123

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aresubjected to a condensation reaction with 3.8 ml of cyanuric fluoride asin Example 122. After the reaction has ended, 4.3 g of m-toluidine areadded at 0°-5° and the pH value is then kept at 5.5-6.0. with 20%strength sodium carbonate solution. The temperature is allowed to riseto 20° in the course of 2 hours and the mixture is subsequently stirredat 20° for 1/2 an hour. The mixture is then cooled to 0°-5°.

A diazonium salt suspension prepared from 8.9 g of2-aminonaphthalene-1-sulphonic acid in the manner described in Example122 is now allowed to run into the mixture and the pH in the couplingmixture is kept at 7.5-8.0. After the coupling has ended, the mixture iswarmed to 20°, the pH value is adjusted to 6.0 with hydrochloric acidand the dyestuff, which has precipitated in the form of crystals, isfiltered off. It is washed with 10% strength sodium chloride solutionand dried at 50° in vacuo.

It corresponds to the formula ##STR37## and dyes cotton, from a longliquor, in bluish-tinged red shades which are distinguished by goodfastness to wet processing.

EXAMPLE 124

8.0 g of 3-aminobenzenesulphonic acid are suspended in 70 ml of water.The suspension is adjusted to pH 3.5 with sodium hydroxide solution andthe mixture is cooled to 0°-5°. 4.2 ml of cyanuric fluoride are addeddropwise in the course of 15 minutes, whilst stirring well, and the pHvalue is kept at 3.2-3.5 with 20% strength sodium carbonate solution.After subsequently stirring for 15 minutes, the reaction has ended and aclear solution has formed. The solution is adjusted to pH 5.5, asolution of 12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acidin 200 ml of water, which has been adjusted to pH 5.5, is now addeddropwise at 0°-5° and the pH value is further kept at 5.5-5.8 with 20%strength sodium carbonate solution.

When the condensation reaction has ended, after a few hours, a diazoniumsalt suspension which has been prepared from 7.0 g of2-aminobenzenesulphonic acid in 100 ml of water and 20 ml ofconcentrated hydrochloric acid with 20 ml of 2N sodium nitrite solutionis slowly added and the pH value in the reaction mixture is kept at7.0-7.5 with 20% strength sodium carbonate solution.

The temperature is kept at 0°-10° and, after 2 hours, is graduallyincreased to 20°. The pH value is adjusted to 6.0, the dyestuff issalted out with 100 g of sodium chloride and the suspension issubsequently stirred for 2 hours. The dyestuff, which corresponds to theformula ##STR38## is filtered off, washed with 15% strength sodiumchloride solution and dried at 50° in vacuo. It dyes cotton in somewhatbluish-tinged red shades.

EXAMPLE 125

If a diazonium salt suspension which has been obtained from 8.9 g of2-aminonaphthalene-1-sulphonic acid in 150 ml of water and 20 ml ofconcentrated hydrochloric acid by diazotisation with 20 ml of 2N sodiumnitrite solution is used in Example 124 instead of the diazotised2-aminobenzenesulphonic acid and the procedure in all the reaction stepsis otherwise completely analogous, a dyestuff of the formula ##STR39##which dyes cotton in more intensely bluish-tinged red shades than thedyestuff of Example 124 is obtained.

EXAMPLE 126

15.1 g of2-(2'-sulphophenylazo)-8-amino-1-hydroxynaphthalene-3,6-disulphonic acidare dissolved, in the form of the trisodium salt, in 300 ml of water.The pH value of the solution is adjusted to 4.5 and the solution iscooled to 0°-5°. 3.1 ml of cyanuric fluoride are then added dropwise,whilst stirring well. The pH value is kept at 4.0-4.5 and, after thedropwise addition, the mixture is stirred for a further 30 minutes.

3.8 g of p-toluidine are dissolved in 10 ml of acetone and the solutionis added dropwise to the difluorotriazinyl-azo dyestuff. The pH value iskept at 5.5-6.0 with sodium carbonate solution and, after 2 hours, thetemperature is allowed to rise gradually to 20°. After the condensationreaction has ended, the dyestuff is salted out with 40 g of sodiumchloride, filtered off and washed with 10% strength sodium chloridesolution. It corresponds to the formula ##STR40## and dyes cotton, froma long liquor, in somewhat bluish-tinged red shades.

EXAMPLE 127

12.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid are firstsubjected to a condensation reaction, in the manner described in Example7, with 3.8 ml of cyanuric fluoride and the resulting intermediateproduct is subjected to a condensation reaction with 7.0 g of4-aminobenzenesulphonic acid. 9.6 g of2-amino-4-acetylaminobenzenesulphonic acid are dissolved in 150 ml ofwater of pH 6. After cooling the solution to 0°-5°, 20 ml ofconcentrated hydrochloric acid are added and 20 ml of 2N sodium nitritesolution are now added dropwise. After the dropwise addition, themixture is stirred for a further 1 hour and any excess of nitrite stillpresent is destroyed with amidosulphonic acid.

The diazonium compound is allowed to run slowly into the solution,prepared above, of the coupling component, and during this a pH value of7.0-7.5 is maintained by adding sodium carbonate solution. Towards theend of the coupling, the temperature is allowed to rise gradually to20°, the pH value is adjusted to 5.5 with hydrochloric acid and thedyestuff is salted out with 100 g of sodium chloride. It is filteredoff, washed with 20% strength sodium chloride solution and dried at 50°in vacuo.

It corresponds to the formula ##STR41## and dyes cotton, from a longliquor, at 40°, in bluish-tinged red colour shades which are fast tolight and wet processing.

EXAMPLE 128

34.1 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 400 ml of water at pH 5.5. After cooling the solution to0°-5°, 9.2 ml of cyanuric fluoride are added dropwise in the course of10 minutes, and during this the pH value in the solution is kept at4.0-4.5 with 20% strength sodium carbonate solution. The mixture issubsequently stirred under the same conditions for 1/2 an hour and 38.0g of the disodium salt of 3-aminonaphthalene-1,5-disulphonic acid arethen introduced. The pH value is adjusted to 5.5 and the temperature isfurther kept at 0°-5°. The condensation reaction has ended after about 1hour.

18.4 g of 2-aminobenzenesulphonic acid are dissolved in 200 ml of waterat pH 6.5. The solution is cooled to 0°-5°, 30 ml of concentratedhydrochloric acid are added and 54 ml of 2N sodium nitrite solution areadded dropwise. The mixture is subsequently stirred at 0°-5° for 1/2-1hour and any excess of nitrite still present is destroyed withamidosulphonic acid solution.

The resulting suspension of the diazo compound is added dropwise, at0°-10°, to the reactive coupling component prepared above and the pHvalue is kept at 7.0-7.5 with 20% strength sodium carbonate solution.After the coupling has ended, the temperature is allowed to rise to 20°,the pH value is adjusted to 6.5 with 10% strength hydrochloric acid andthe dyestuff is slowly salted out with 200 g of sodium chloride. Aftersubsequently stirring the suspension for half an hour, the dyestuff isfiltered off, washed with 15% strength sodium chloride solution anddried at 40° in vacuo. In the form of the free acid, it corresponds tothe formula ##STR42##

50 g of cotton hanks are dyed in 1 liter of a dye liquor, which contains1.5 g of the above dyestuff, by heating the liquor to 40° in the courseof 30 minutes, adding 50 g of sodium sulphate in several portions, thenadding 20 g of sodium carbonate and treating the material at thistemperature for 60 minutes. After rinsing, soaping at the boil anddrying, a bluish-tinged red dyeing which has good fastness to light andis very fast to wet processing is obtained.

EXAMPLE 129

34.1 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 400 ml of water at pH 5.5. After cooling the solution to0°-5°, 9.2 ml of cyanuric fluoride are added dropwise in the course of10 minutes, and during this the pH value in the solution is kept at4.0-4.5 by adding 20% strength sodium carbonate solution dropwise. Thesolution is subsequently stirred at this pH value and at 0°-5° for 1/2an hour and 24.5 g of 5-aminonaphthalene-2-sulphonic acid are thenadded. The ph value of the solution kept at 5.5-6.0 with sodiumcarbonate solution and the temperature is gradually increased to 20° inthe course of 2 hours. After the condensation reaction has ended, themixture is again cooled to 0°-10° and the suspension of a diazoniumcompound which has been obtained from 18.4 g of 2-aminobenzenesulphonicacid in 200 ml of water and 30 ml of concentrated hydrochloric acid with54 ml of 2N sodium nitrite solution in the manner shown in the Exampleis now added.

The pH value is adjusted to 7.0-7.5 for the coupling and is further keptwithin these limits with 20% strength sodium carbonate solution. Thetemperature is allowed to rise to 20° in the course of 3 hours. Afterthe coupling has ended, the pH value is adjusted to 6.5 and thedyestuff, which has already precipitated, is further salted outgradually with 100 g of sodium chloride. The dyestuff is filtered off,washed with 7% strength sodium chloride solution and dried at 40° invacuo. In the form of the free acid, it corresponds to the formula##STR43##

When this dyestuff is dyed onto cotton by the process of Example 1,bluish-tinged red dyeings which are fast to wet processing and light arelikewise obtained.

EXAMPLE 130

If 24.5 g of 5-aminonaphthalene-1-sulphonic acid are used in Example 2instead of 5-aminonaphthalene-2-sulphonic acid and the procedure in allthe process steps is analogous, a dyestuff of the formula ##STR44##which dyes cotton, from a long liquor by the dyeing process of Example1, in a bluish-tinged red shade is obtained.

EXAMPLE 131

34.1 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 400 ml of water at pH 5.5. The solution is reacted with 9.2ml of cyanuric fluoride at 0°-5° in the manner indicated in Example 1.After the reaction has ended, 33.4 g of5-aminonaphthalene-1,3-disulphonic acid are added to the solution andthe pH value is kept at 5.5 with 20% strength sodium carbonate solution.The temperature is allowed to rise to 20° in the course of 2 hours.After this period, the condensation reaction of the difluorotriazinylcomponent with the aminonaphthalenedisulphonic acid had ended. Thesolution is again cooled to 0°-10° and a suspension of a diazonium saltwhich has been prepared from 18.4 g of 2-aminobenzenesulphonic acid in200 ml of water and 30 ml of concentrated hydrochloric acid with 54 mlof 2N sodium nitrite solution as in Example 1 is gradually added. Duringthe introduction of the diazonium compound, a pH value of 7.0-7.5 ismaintained in the coupling mixture with 20% strength sodium carbonate.The temperature is then allowed to rise to 20° in the course of 3 hours,whilst further controlling the pH. After the coupling has ended, the pHvalue is adjusted to 6.5, the dyestuff is salted out with 200 g ofsodium chloride and the suspension is subsequently stirred for 2 hours.The dyestuff is filtered off, washed with 20% strength sodium chloridesolution and covered twice with 15% strength sodium chloride solution.After drying at 40° in vacuo, a dyestuff of the formula ##STR45## whichdyes cotton, from a long liquor, in bluish-tinged red shades which arefast to wet processing and light is obtained.

EXAMPLE 132

34.1 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid are firstreacted, in the manner shown in Example 1, with 9.2 ml of cyanuricfluoride at 0°-5° and pH 4.0-4.5 and 33.4 g of7-aminonaphthalene-1,3-disulphonic acid are then added to the resultingsolution of the difluorotriazinyl compound formed. The pH value is keptat 5.5-6.0 with 20% strength sodium carbonate solution.

23.8 g of 2-aminonaphthalene-1-sulphonic acid are dissolved in 280 ml ofwater at pH 7. The solution is cooled to 0°-5°, 30 ml of concentratedhydrochloric acid are added and 54 ml of 2N sodium nitrite solution areadded dropwise in the course of 1 hour. After subsequently stirring themixture for 1/2 an hour, excess nitrite is removed with amidosulphonicacid solution.

The diazonium compound is now allowed to run gradually into the solutionof the coupling component prepared above, and during this the pH valueis kept at 7.5-8.0 with 20% strength sodium carbonate solution. Thetemperature is allowed to rise to 20° in the course of 2 hours, and,after the coupling has ended, the pH value is adjusted to 6.0, and thedyestuff is salted out with 210 g of sodium chloride. After subsequentlystirring the mixture for several hours, the dyestuff is filtered off,washed with 20% strength sodium chloride solution and dried at 40° invacuo. In the form of the free acid, it corresponds to the formula##STR46## and dyes cotton, from a long liquor, in distinctlybluish-tinged red shades which are fast to wet processing and light.

EXAMPLE 133

34.1 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aresubjected to a condensation reaction, analogously to Example 1, with 9.2ml of cyanuric fluoride at 0°-5° and pH 4.0-4.5. 24.5 g of6-aminonaphthalene-2-sulphonic acid are added to the resulting solutionand the pH value is then kept at 5.5-6.0 with 20% strength sodiumcarbonate solution. The temperature is increased to 20° in the course of3 hours and the resulting solution is cooled to below 10°.

32.4 g of 2-aminonaphthalene-1,5-disulphonic acid are dissolved in 300ml of water at pH 6.0. This solution is cooled to 0°-5°, 30 ml ofconcentrated hydrochloric acid are added and the amine is thendiazotised with 54 ml of 2N sodium nitrite solution. After subsequentlystirring for 1 hour, excess nitrite is removed with amidosulphonic acid.

The diazonium salt solution is now gradually added to the couplingcomponent prepared above and the pH value in the coupling mixture iskept at 7.0-7.5 with 20% strength sodium carbonate solution. After thecoupling has ended, the temperature is allowed to rise to 20°, the pHvalue is adjusted to 6.0 with dilute hydrochloric acid and the dyestuffis salted out with 220 g of sodium chloride. After subsequently stirringthe suspension for 2-3 hours, the dyestuff is filtered off, washed with15% strength sodium chloride solution and dried at 40° in vacuo. Itcorresponds to the formula ##STR47## and dyes cotton, from a longliquor, in quite bluish-tinged red shades which are fast to wetprocessing.

EXAMPLE 134

34.1 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aresubjected to a condensation reaction, as described in Example 1, with9.2 ml of cyanuric fluoride at 0°-5° and pH 4.0-4.5. 24.5 g of4-aminonaphthalene-1-sulphonic acid are added to the resulting solutionand the pH value is then kept at 5.5-6.0 with 20% strength sodiumcarbonate. The condensation reaction is brought to completion byallowing the temperature to rise slowly to 20° in the course of 3 hours,and the mixture is then again cooled to below 10°. 27.1 g of2-aminobenzene-1,4-disulphonic acid are dissolved in 200 ml of water atpH 6. The solution is cooled to 0°-5° and 30 ml of concentratedhydrochloric acid are added. 54 ml of 2N sodium nitrite solution are nowallowed to run into the solution in the course of 1 hour and the mixtureis subsequently stirred for a further 1 hour. Thereafter, any excess ofnitrite is destroyed with amidosulphonic acid.

The resulting diazonium compound is added to the solution, preparedabove, of the coupling component at 0°-10° and the pH value in thereaction mixture is kept at 7.0-7.5 with sodium carbonate solution.After adding the diazonium salt solution, the mixture is further stirredat this pH value for 1 hour, the temperature is then allowed to rise to20° and the pH value is adjusted to 6.0 with dilute hydrochloric acid.The dyestuff is salted out with 200 g of sodium chloride, filtered offand washed with 15% strength sodium chloride solution. After drying invacuo at 40°, a product is obtained which dyes cotton, from a longliquor, in bluish-tinged red shades which are fast to wet processing,which may be assigned the formula ##STR48##

EXAMPLE 135

34.1 g of 1-amino-8-hydroxynaphthalene-4,6-disulphonic acid aredissolved in 400 ml of water at pH 6.0. After cooling the solution to0°-5°, the pH value is adjusted to 3.5 with hydrochloric acid. 9.2 ml ofcyanuric fluoride are now added dropwise in the course of 10 minutes andthe pH value is kept at 3.5-4.0 with 20% strength sodium carbonatesolution. The mixture is subsequently stirred under the conditionsindicated for a further 15 minutes and 24.5 g of6-aminonaphthalene-1-sulphonic acid are then added to the resultingsolution. The condensation reaction between the difluorotriazinylcompound and the aminonaphthalenesulphonic acid is carried out byadjusting and maintaining a pH value of 5.5-6.0, the temperature beingallowed to rise from 0°-5° to 20° in the course of 3 hours.

18.4 g of 2-aminobenzenesulphonic acid are dissolved in 200 ml of waterat pH 6.5. After adding 30 ml of concentrated hydrochloric acid andcooling the mixture to 0°-5°, the amine is diazotised with 54 ml of 2Nsodium nitrite solution and the excess of nitrite is destroyed withamidosulphonic acid solution.

The resulting diazonium salt suspension is now gradually added to thecoupling component prepared above and the pH value is kept at 7.5-8.0with 20% strength sodium carbonate solution and the temperature is keptbelow 10°. The mixture is further stirred for 1 hour and the temperatureis then allowed to rise to 20° in the course of a further hour. Afterthe coupling has ended, the pH value is adjusted to 6.0 with dilutehydrochloric acid and the dyestuff is salted out with 180 g of sodiumchloride. It is filtered off, washed with 15% strength sodium chloridesolution and dried at 40° in vacuo.

In the form of the free acid, it corresponds to the formula ##STR49##and dyes cotton, from a long liquor, in bluish-tinged red shades whichare fast to wet processing.

Dyestuffs of the formula ##STR50## can be synthesised in an analogousmanner when the aminohydroxynaphthalenedisulphonic acids given in TableI, column 2, are subjected to a condensation reaction with cyanuricfluoride, the resulting intermediate products are reacted with theaminonaphthalenesulphonic acids given in the third column and theproducts are then coupled with the diazotised amines D-NH₂ given in thefourth column.

                                      TABLE I                                     __________________________________________________________________________     Example No.                                                                        1-Amino-8-hydroxynaphthalene- disulphonic acid                                                ##STR51##          D-NH.sub.2                           __________________________________________________________________________    136  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          1-sulphonic acid  acid                                   137  1-Amino-8-hydroxynaphthalene-                                                                 1-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          1-sulphonic acid  acid                                   138  1-Amino-8-hydroxynaphthalene-                                                                 8-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          1-sulphonic acid  acid                                   139  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          2-sulphonic acid  acid                                   140  1-Amino-8-hydroxynaphthalene-                                                                 7-Methylaminonaphtha-                                                                           2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          lene-2-sulphonic acid                                                                           acid                                   141  1-Amino-8-hydroxynaphthalene-                                                                 7-Ethylaminonaphtha-                                                                            2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          lene-2-sulphonic acid                                                                           acid                                   142  1-Amino-8-hydroxynaphthalene-                                                                 8-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          2-sulphonic acid  acid                                   143  1-Amino-8-hydroxynaphthalene-                                                                 7-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          1,3-disulphonic acid                                                                            acid                                   144  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          1,3-disulphonic acid                                                                            acid                                   145  1-Amino-8-hydroxynaphthalene-                                                                 4-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          2,6-disulphonic acid                                                                            acid                                   146  1-Amino-8-hydroxynaphthalene-                                                                 7-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          1,3,5-trisulphonic acid                                                                         acid                                   147  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     4,6-disulphonic acid                                                                          2-sulphonic acid  acid                                   148  1-Amino-8-hydroxynaphthalene-                                                                 5-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     4,6-disulphonic acid                                                                          1-sulphonic acid  acid                                   149  1-Amino-8-hydroxynaphthalene-                                                                 7-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     4,6-disulphonic acid                                                                          1,3-disulphonic acid                                                                            acid                                   150  1-Amino-8-hydroxynaphthalene-                                                                 5-Aminonaphthalene-                                                                             2-Aminonaphthalene-                         4,6-disulphonic acid                                                                          1,3-disulphonic acid                                                                            1-sulphonic acid                       151  1-Amino-8-hydroxynaphthalene-                                                                 5-Aminonaphthalene-                                                                             2-Aminobenzene-1,4-                         4,6-disulphonic acid                                                                          1-sulphonic acid  disulphonic acid                       152  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Aminonaphthalene-                         4,6-disulphonic acid                                                                          1-sulphonic acid  1,5-disulphonic acid                   153  1-Amino-8-hydroxynaphthalene-                                                                 3-Aminonaphthalene-                                                                             2-Aminonaphthalene-                         4,6-disulphonic acid                                                                          1,5-disulphonic acid                                                                            1-sulphonic acid                       154  1-Amino-8-hydroxynaphthalene-                                                                 7-Aminonaphthalene-                                                                             2-Amino-4-acetylbenzene-                    4,6-disulphonic acid                                                                          1,3-disulphonic acid                                                                            sulphonic acid                         155  1-Amino-8-hydroxynaphthalene-                                                                 7-Aminonaphthalene-                                                                             2-Amino-5-methoxy-                          4,6-disulphonic acid                                                                          1,3,5-trisulphonic                                                                              benzenesulphonic acid                                       acid                                                     156  1-Amino-8-hydroxynaphthalene-                                                                 7-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     2,4-disulphonic acid                                                                          1,3-disulphonic acid                                                                            acid                                   157  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     2,4-disulphonic acid                                                                          2-sulphonic acid  acid                                   158  1-Amino-8-hydroxynaphthalene-                                                                 3-Aminonaphthalene-                                                                             2-Aminonaphthalene-1-                       2,4-disulphonic acid                                                                          1,5-disulphonic acid                                                                            sulphonic acid                         159  1-Amino-8-hydroxynaphthalene-                                                                 4-Aminonaphthalene-                                                                             2-Aminonaphthalene-1-                       3,6-disulphonic acid                                                                          2,7-disulphonic acid                                                                            sulphonic acid                         160  1-Amino-8-hydroxynaphthalene-                                                                 7-Aminonaphthalene-                                                                             2-Aminonaphthalene-1-                       3,6-disulphonic acid                                                                          1,3,5-trisulphonic                                                                              sulphonic acid                                              acid                                                     161  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Aminonaphthalene-1-                       3,6-disulphonic acid                                                                          1-sulphonic acid  sulphonic acid                         162  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Aminonaphthalene-1-                       3,6-disulphonic acid                                                                          2-sulphonic acid  sulphonic acid                         163  1-Amino-8-hydroxynaphthalene-                                                                 7-Methylaminonaphtha-                                                                           2-Aminonaphthalene-                         3,6-disulphonic acid                                                                          lene-2-sulphonic acid                                                                           1-sulphonic acid                       164  1-Amino-8-hydroxynaphthalene-                                                                 7-Butylaminonaphtha-                                                                            4-Aminobenzene-1,3-                         3,6-disulphonic acid                                                                          lene-2-sulphonic acid                                                                           disulphonic acid                       165  1-Amino-8-hydroxynaphthalene-                                                                 5-Aminonaphthalene-                                                                             2-Amino-5-acetylamino-                      3,6-disulphonic acid                                                                          1,3-disulphonic acid                                                                            benzenesulphonic acid                  166  1-Amino-8-hydroxynaphthalene-                                                                 5-Aminonaphthalene-                                                                             3-Aminonaphthalene-                         3,6-disulphonic acid                                                                          1-sulphonic acid  1,5-disulphonic acid                   167  1-Amino-8-hydroxynaphthalene-                                                                 3-Aminonaphthalene-                                                                             2-Amino-5-chloroben-                        3,6-disulphonic acid                                                                          1,5-disulphonic acid                                                                            zenesulphonic acid                     168  1-Amino-8-hydroxynaphthalene-                                                                 5-Aminonaphthalene-                                                                             2-Aminonaphthalene-                         3,5-disulphonic acid                                                                          1,3-disulphonic acid                                                                            1-sulphonic acid                       169  1-Amino-8-hydroxynaphthalene-                                                                 8-Aminonaphthalene-                                                                             2-Aminobenzenesulphonic                     3,5-disulphonic acid                                                                          2-sulphonic acid  acid                                   170  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Amino-4-chloroben-                        3,5-disulphonic acid                                                                          1,3-disulphonic acid                                                                            zenesulphonic acid                     171  1-Amino-8-hydroxynaphthalene-                                                                 6-Aminonaphthalene-                                                                             2-Amino-5-methylben-                        3,5-disulphonic acid                                                                          1-sulphonic acid  zenesulphonic acid                     172  1-Amino-8-hydroxynaphthalene-                                                                 7-Isobutylaminonaphtha-                                                                         2-Aminobenzenesulphonic                     3,6-disulphonic acid                                                                          lene-2-sulphonic acid                                                                           acid                                   __________________________________________________________________________

EXAMPLE 173

37.3 g of 3-aminonaphthalene-2,7-disulphonic acid are dissolved in 300ml of water at pH 7. The pH value is adjusted to 5.0, the solution iscooled to 0°-5° and 11.0 ml of cyanuric fluoride are now added dropwisein the course of 15 minutes. The pH value is kept at 5.0-5.5 with 20%strength sodium carbonate solution. After the dropwise addition, themixture is subsequently stirred for a further 20 minutes at 0°-5° and pH5.0 and a solution, adjusted to pH 5, of 34.1 g of1-amino-8-hydroxynaphthalene-3,6-disulphonic acid in 400 ml of water isthen allowed to run into the resulting solution. The pH value is kept at5.5-6.0 with 20% strength sodium carbonate solution and the condensationreaction between the difluorotriazinylaminonaphthalenedisulphonic acidand the aminohydroxynaphthalenedisulphonic acid is brought to completionby subsequently stirring the mixture for several hours.

A diazonium salt suspension which has been prepared from 18.4 g of2-aminobenzenesulphonic acid in 200 ml of water and 30 ml ofconcentrated hydrochloric acid with 54 ml of 2N sodium nitrite solutionaccording to Example 1 is now added to the solution, prepared above, ofthe coupling component at 0°-10° and the pH value in the reactionmixture is kept at 7.0-7.5 by means of 20% strength sodium carbonatesolution. The temperature is allowed to rise gradually to 20° in thecourse of 2 hours and after the coupling has ended the pH value isadjusted to 6.5.

The dyestuff is salted out by adding 270 g of sodium chloride and, aftersubsequently stirring the mixture for a short time, is filtered off,washed with 15% strength sodium chloride solution and dried at 40° invacuo.

In the form of the free acid, it corresponds to the formula ##STR52##and it dyes cotton, from a long liquor, in bluish-red shades which arefast to wet processing and light.

Dyestuffs of the formula ##STR53## can be built up in an analogousmanner if, instead of the 3-aminonaphthalene-2,7-disulphonic acid, theaminonaphthalenesulphonic acids of the formula ##STR54## listed incolumn 2 of Table II are subjected to a condensation reaction withcyanuric fluoride, the difluorotriazinylaminonaphthalenesulphonic acidsformed are subjected to a condensation reaction with the amino group of1-amino-8-hydroxynaphtha-lenedisulphonic acids (column 3) and theresulting products, which can undergo coupling, are coupled with thediazotised amines D--NH₂ of column 4.

                                      TABLE II                                    __________________________________________________________________________     Example No.                                                                        ##STR55##         1-Amino-8-hydroxynaphthalene- disulphonic                                                      D-NH.sub.2                           __________________________________________________________________________    174  2-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             1-sulphonic acid  3,6-disulphonic acid                                                                          sulphonic acid                         175  2-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 1-Aminobenzene-                             1,5-disulphonic acid                                                                            3,6-disulphonic acid                                                                          sulphonic acid                         176  2-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             1,7-disulphonic acid                                                                            3,6-disulphonic acid                                                                          sulphonic acid                         177  4-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             1,3-disulphonic acid                                                                            3,6-disulphonic acid                                                                          sulphonic acid                         178  1-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             2-sulphonic acid  3,6-disulphonic acid                                                                          sulphonic acid                         179  6-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             2-sulphonic acid  3,6-disulphonic acid                                                                          sulphonic acid                         180  4-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             1-sulphonic acid  3,6-disulphonic acid                                                                          sulphonic acid                         181  4-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-1,4-                         2-sulphonic acid  3,6-disulphonic acid                                                                          disulphonic acid                       182  3-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             1-sulphonic acid  3,6-disulphonic acid                                                                          sulphonic acid                         183  7-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             2-sulphonic acid  3,6-disulphonic acid                                                                          sulphonic acid                         184  2-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminonaphthalene-                         1-sulphonic acid  3,6-disulphonic acid                                                                          1-sulphonic acid                       185  2-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminonaphthalene-                         1,5-disulphonic acid                                                                            3,6-disulphonic acid                                                                          1-sulphonic acid                       186  7-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminonaphthalene-                         1,3,6-trisulphonic acid                                                                         3,6-disulphonic acid                                                                          1-sulphonic acid                       187  2-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminonaphthalene-                         1,5-disulphonic acid                                                                            4,6-disulphonic acid                                                                          1-sulphonic acid                       188  3-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminonaphthalene-                         1,5-disulphonic acid                                                                            4,6-disulphonic acid                                                                          1-sulphonic acid                       189  2-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             1-sulphonic acid  4,6-disulphonic acid                                                                          sulphonic acid                         190  3-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             2,7-disulphonic acid                                                                            4,6-disulphonic acid                                                                          sulphonic acid                         191  3-Aminonaphthalene-                                                                             1-Amino-8-hydroxynaphthalene-                                                                 2-Aminobenzene-                             2,6-disulphonic acid                                                                            4,6-disulphonic acid                                                                          sulphonic acid                         __________________________________________________________________________

EXAMPLE 192

25.0 g of2-(2'-sulphophenylazo)-8-amino-1-hydroxynaphthalene-3,6-disulphonic acidare dissolved, in the form of the trisodium salt, in 500 ml of water.The pH value of the solution is adjusted to 4.5 and the solution iscooled to 0°-5°. 5.0 ml of cyanuric fluoride are now added dropwise inthe course of 10 minutes and the pH value is kept at 4.0-4.5 with 20%strength sodium carbonate solution. The reaction is brought tocompletion by subsequently stirring the mixture for 10 minutes.

13.1 g of 7-aminonaphthalene-1-sulphonic acid are then added to thesolution and the pH value is adjusted to 5.5-6.0. The mixture is nowfurther stirred at 0°-5° and pH 5.5-6.0 until no moredifluorotriazinyl-azo dyestuff can be detected in a chromatogram. Themixture is then warmed to 20°. The dyestuff is salted out with 180 g ofsodium chloride, filtered off and washed with 15% strength sodiumchloride solution. It is dried at 40° in vacuo. The dyestuff dyescotton, from a long liquor by the dyeing process of Example 1, inbluish-tinged red shades which have good fastness to wet processing andlight. In the form of the free acid, it corresponds to the formula

We claim:
 1. Reactive dyestuffs of the formulawherein R is ##STR57## Dis a naphthyl substituent which is unsubstituted or substituted by 1 to3 sulfo groups, R₁ is hydrogen or alkyl, R₂ is halogen, alkyl, alkoxy oracetylamino and n is 1, 2 or
 3. 2. Reactive dyestuffs according to claim1, characterised in that D represents 1-sulpho-2-naphthyl,1,5-disulpho-2-naphthyl, 1,7-disulpho-2-naphthyl,1,5-disulpho-3-naphthyl, 2,6-disulpho-3-naphthyl,3,6-disulpho-2-naphthyl, 1,3-disulpho-7-naphthyl,1,3-disulpho-6-naphthyl, 1-sulpho-4-naphthyl, 1-sulpho-5naphthyl,1-sulpho-6-naphthyl, 3,7-disulpho-1-naphthyl, 1,3-disulpho-4-naphthyl,1,3,5-trisulpho-6-naphthyl, 1,3,6-trisulpho-7-naphthyl or1,3,6-trisulpho-4-naphthyl.
 3. Reactive dyestuffs of the formula##STR58## wherein D, R₁, R₂ and n have the meaning indicated in claim 1.4. Reactive dyestuffs of the formula ##STR59## wherein D, R₁, R₂ and nhave the meaning indicated in claim
 1. 5. ##STR60## wherein R₁, R₂ and nhave the meaning indicated in claim
 1. 6. Reactive dyestuffs of theformula ##STR61## wherein Y is, 4-acetylaminophenyl.